Stable emulsion



atente' 2.203.641 STABLE EMULSION No Drawing. Application October 23,1937, Serial No. 170,595

16 Claims.

The invention relates, in general, to emulsified metallic soaps and, inparticular, to emulsions of water-insoluble salts of naphthenic acids ornaphthenic acid esters.

The water-insoluble soaps, and more particularly the water-insolublenaphthenates of the polyvalent metals and derivatives,thereof, have beenfound to possess valuable properties and characteristics which adaptthem to many praclo tical and potential uses in the industrial arts.These salts are admirably suited for preserving fibrous materials, suchas wood, paper, textiles, etc., against rot and decay and forwaterproofing and weatherproofing the above-named fibrous as well asporous materials such as concrete, stone, etc. These salts have alsofound extensive use in the manufacture of cutting oils, sprays,insecticides, fungicides, germicides, and the like. In the preparationof solutions or compositions containing the polyvalent metal salts ofnaphthenic acids or derivatives thereof, it has been necessary to employorganic solvents in dissolving, swelling or dispersing these salts inview of their extreme resistance to wetting by water and water-solublewetting and emusifying agents. This factor has restricted the use ofthese salts as in many instances the presence of organic solvents isprohibited or highly undesirable. Moreover,.organic solvents areexpensive and greatly increase the cost of manufacturing compositions ofthe type referred to above.

The general object of the invention is to obviate the foregoing andother disadvantages.

A specific object of the invention is to provide a fluid, organicsolvent-free composition containing a polyvalent metal salt ofnaphthenic acids.

Another object of the invention is to dispense with the use of organicsolvents in the. preparation of compositions containing polyvalent metalsalts of naphthenic acids.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

It has now been discovered that polyvalent metal salt of naphthenicacids or naphthenic 4:;- acid esters may -be emulsified to form stableoilin-water type emulsions. According to the invention such emulsionsare produced by employing as the emulsifier a sulfation product of anester of naphthenic acids with an unsaturated 50 compound containing 8or more carbon atoms selected from the group consisting of monohydricfatty alcohols, hydroxy fatty acids and hydroxy fatty esters.

The invention accordingly comprises the several 55 steps and relation ofone or more of such steps with respect to each of the others, and acomposition of matter possessing the characteristics, properties andrelation of components, all of which will be exemplified in thefollowing detailed disclosure, and the scope of the invention will beindicated in the claims.

The expression naphthenic acids" is employed herein to connote themixture of acids of that name currently obtained in petroleum refining,as well as the naphthenic acid or acids which are synthetically preparedor otherwise obtained. It is preferred, however, to use the naphthenicacids derived from the refining of petroleum in view of their relativelylow cost.

The metallic salts which can be emulsified according to the inventioncomprise the naphthenates of polyvalent metals, such for example, asnaphthenates of lead, copper, aluminum, tin zinc, mercury, etc, orderivatives of these soaps, such as the lead, copper, aluminum, etc.salts of an ester of naphthenic acids with ricinoleic acid or castoroil, or any combination of two or more of these or other salts. For thepurpose of this invention the expression salt of a ,naphthenic compound"will be used to generically include the straight naphthenic acid saltsas well as the salts of naphthenic acid esters of the afore mentionedtype. The lead and copper naphthenates or lead and copper salts ofnaphthenic acid esters, as well as a combination of these two salts, areparticularly well suited for emulsification according to the presentinvention. The metallic naphthenates or derivatives thereof to beemulsified according to the invention may be produced by the reaction ofnaphthenic acids or esters on suitable salts of various metals, or byanyother suitable method known to the art.

The production of stable emulsions of the above referred to naphthenatesmay be achieved, accordin to the invention, through the use of new andspecially prepared emulsifiers which comprise the sulfated esters ofnaphthenic acids with an unsaturated compound, containing 8 or morecarbon atoms, selected from the group consisting of fatty alcohols, suchas oleyl alcohol, hydroxy fatty acids, such as ricinoleic acid, andhydroxy fatty esters, such as castor oil. In practice the sulfatedesters of naphthenic acids with castor oil or ricinoleic acid haveproven to be of particular value and their use in instant case is highlypreferred. The new emulsifiers per se, which are employed in carryingout the present invention, are fully disclosed and claimed in myco-pending'application for U. S. Letters Patent, Serial Number 170,596,filed October 23, 1937.

For a'fuller understanding of the nature and objects of the invention,reference should'be-had to the following examples which are given merelyto illustrate some of the compositions of the invention and the methodof making the same, and in no way should they be construed in a limitingsense.

Example I One part of lead naphthenate, prepared by known methods, ismixed with two parts of an emulsifier consisting of the sulfated esterof naphthenic acid and castor oil.

When one part of this mixture is stirred into 9 parts of water, a stableemulsion is formed. The lead emulsion thus produced can beused inemulsifying cutting oils, in metal stamping or drawing lubricants or inother industrial applications.

Example If One part of a lead salt of an ester of naphthenic acids withricinoleic acid is mixed with two parts of the sulfation product of anester of naphthenic acids with ricinoleic acid. This mixture is thenstirred into the desired quantity of water.

Example V A mixture of one part aluminum naphthenate and three partssulfated oleyl naphthenate is emulsified into water to.produce a 10%emulsion. This emulsion is useful in textile treatments and forwater-proofing of various fibrous and mineral materials.

Example VI The oleyl naphthenate of Example V is replaced by thesulfated ester of naphthenic acids with ricinoleic acid.

The proportions of metallic naphthenates and their derivatives andemulsifiers given in the above examples are merely illustrative, and itmust be understood that emulsions satisfactory for various purposes canbe produced with the use of a greatly reduced percentage of emulsifierin the finished mixture. Such emulsions may not remain stable as long asemulsions containing a higher percentage of emulsifier, but it is notalways desirable to have a perfectly stable emulsion, as for example, inthe field of insecticides, the use of emulsions having reduced ortemporary stability is desirable. For such applications, the percentageof emulsifier in the mixture can therefore be greatly reduced. While forall practical intents and purposes the objects of the invention .may befully realized by the use of .the hereinbefore disclosed emulsifiers,whether containing moisture or not, it has been found that the stabilityof the emulsions of the invention may be enhanced if the anhydrous formof the emulsifier s mp o d 1 p The percentage of water in the emulsioncan also be varied within wide limits, according to the'type andviscosityof emulsion which seems desirable for the particular usecontemplated. Such emulsions, for example, may contain as little as 50%water or less, while others may be made with as much water as is deemednecessary 5 or desirable. thenate emulsions or emulsion of theirderivatives produced according to this invention are of the oil-in-watertype, it is evident that their dilution with water offers no difiiculty.10

Since the insoluble metallic naph- Since certain changes in carrying outthe above process and certain modifications in the composition whichembody the invention may be made without departing from its scope; it isintended that all matter contained in the above descrip- 15 tion shallbe interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended tocover all of the generic and specific features of the invention hereindescribed 20 and all statements of the scope of the invention which, asa matter of language, might be said to fall therebetween; and that theyare intended to be inclusive in scope and not exclusive, in that ifdesired other materials may be added to my 25 novel composition ofmatter herein claimed without departing from the spirit of theinvention. Particularly it is to be understood that in said claimsingredients or components recited in the singular are intended toinclude compatible mix- 30 tures of said ingredients wherever the sensepermits.

Having described my invention, what I claim as new and desire to secureby LettersPatent is:

l. A stable emulsion comprising a polyvalent-35 metal salt of anaphthenic compound, water and a sulfation product of an ester ofnaphthenicacids with an unsaturated compoundmontaining 8 or more carbonatoms, selected from the group consisting of monohydric fatty alcohols,hydroxy 40 fatty acids and hydroxy fatty esters.

2. A stable emulsion comprising a lead naphthenate, water and asulfation product of an ester of naphthenic acids with an unsaturatedcompound, containing 8 or more carbon atoms, se- 45 lected from thegroup consisting of monohydric fatty alcohols, hydroxy fatty acids andhydroxy fatty esters.

3. A stable emulsion comprising a copper naphthenate, water and asulfation product of an ester 5 of naphthenic acids with an unsaturatedcompound, containing. 8 or more carbon atoms, selected from the groupconsisting of monohydric fatty alcohols, hydroxyfatty acids and hydroxyfatty esters. 55

4. A stable emulsion comprising a lead naphthenate, copper naphthenate,water and a sulfation product of an ester of naphthenic acids with anunsaturated compound, containing 8 or more carbon atoms, selected fromthe group consisting go of monohydric fatty alcohols, hydroxy fattyacids and hydroxy fatty esters.

5. A stable emulsion comprising a polyvalent metal salt of a naphtheniccompound, water and g a sulfation product of an ester of naphthenic 05acids with oleyl alcohols.

6. A stable emulsion comprising a polyvalent metal salt of a naphtheniccompound, water and a sulfation product of an ester of naphthenic acidswith ricinoleic acid. 70

'1. A stable emulsion comprising a polyvalent metal salt of a naphtheniccompound, water and a sulfation product of an -ester of'naphthenic acidswith castor oil.

8. A stable emulsion cor nprising lead naphj thenate, water and asulfation product of'au ester of naphthenic acids with castor oil.

' naphthenate, water and a sulfation product of an ester of-naphthenicacids withoieyl alcohol.

11. A process of producing stable was which comprises mixing apoiyvaient metal salt of a naphthenic compound with a sulfated ester ofnaphthenic acids with an unsaturated compound selected from the groupconsisting of monohydric fatty alcohols, hydroxy fatty acids and hydroxyfatty esters and stirring the intofan aqueous vehicle.

12. A process according to claim 11, wherein an anhydrous sulfated esteris employed.

13. A water-dispersible composition comprising a. polyvalent metal saltof a naphthenic. compound and a suli'ation product of an ester of'naphthenic acids with an unsaturated und containing 8 or more carbonatoms selected from the group consisting of monohydric fatty alcohols,hydroxy fatty acids and hydrow 14. A water-dispersible compositioncomprising lead naphthenate and a sulfation product of an esterofnaphthenic acids with an unsaturated compound containing 8 or morecarbon atoms selected from the group consisting of monohydric fattyalcohols; hydroxy fatty acids and hydroxy fattyesters. 15. Awater-dispersible com comprising copper naphthenate and a suifationproduct of an ester of naphthenic acids with an unsaturated compoundcontaining 8 or more carbon atoms selected from the group consisting ofmonohydric fatty alcohols, hydroxy. fatty acids and hydroxy fattyesters. 1'.

fatty more carbon atoms selected from the group consisting of monohydricfatty alcohols. hydroxy fatty acids and hydroxy fatty esters.

